CN110183642B - Catalyst for synthesis of polyoxyethylene fatty acid ester - Google Patents
Catalyst for synthesis of polyoxyethylene fatty acid ester Download PDFInfo
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- CN110183642B CN110183642B CN201910437682.5A CN201910437682A CN110183642B CN 110183642 B CN110183642 B CN 110183642B CN 201910437682 A CN201910437682 A CN 201910437682A CN 110183642 B CN110183642 B CN 110183642B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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Abstract
The invention relates to a catalyst for synthesizing polyoxyethylene fatty acid ester, which mainly aims to solve the problem of high content of polyethylene glycol in products in the prior artThe technical scheme is as follows: a catalyst for the synthesis of polyoxyethylene fatty acid ester, the catalyst comprising a quaternary ammonium compound and a transition metal oxide, the transition metal oxide comprising a metal selected from the group consisting of CoO, ZnO and La2O3The invention solves the technical problem well by at least one of the substance groups.
Description
Technical Field
The invention relates to a catalyst for synthesizing polyoxyethylene fatty acid ester, in particular to a catalyst for preparing polyoxyethylene fatty acid ester by taking fatty acid and ethylene oxide as raw materials through polymerization reaction.
Background
The polyoxyethylene fatty acid ester is a very important nonionic surfactant and has a wide application range, such as the polyoxyethylene oleate (3-5) ester is used as an antistatic agent in textile processing and synthetic fiber production; as softeners, lubricants for tanning leather on leather; as an emulsifier in ink manufacture; the emulsifier is used as an emulsifier of cutting oil in metal processing, and is used as an emulsifier and a dispersant of a metal cleaning agent and a detergent solvent. The oleic acid polyoxyethylene (10-15) ester is used as a special detergent and a dyeing assistant in textile industry; in leather processing, as a neat's foot oil emulsifier; in the paint and printing industry, the pigment grinding aid is used as a pigment and an ink grinding aid; in the paper industry, as a paper re-lubricant; in the rubber industry, as dispersants; as plasticizers in the plastics industry; also as an emulsifier for pesticides, glass, paraffin, etc. In conclusion, the fatty acid polyoxyethylene ester has wide industrial application prospect and great development value.
At present, two methods for synthesizing polyoxyethylene fatty acid ester are widely used in industry, namely an esterification method and an ethoxylation method, wherein the esterification method comprises the steps of adding quantitative fatty acid, polyethylene glycol and a proper amount of acid catalyst into a stirred tank reactor together, heating and dehydrating at a certain temperature, and determining a reaction end point by measuring an acid value, but the dehydration process and the reaction end point of the esterification reaction are difficult to grasp, so that the color and luster of a product are relatively deep. In contrast, the ethoxylation process is advantageous over the fat process. Firstly, adding a certain amount of fatty acid and a conventional alkaline catalyst into a reactor, introducing a certain amount of ethylene oxide at a certain temperature after vacuum pretreatment, and then curing and neutralizing. The ethoxylation process has the advantages of easy control of the end point, stable product quality, good color, etc. However, the fatty acid polyoxyethylene ester synthesized by the two methods contains polyethylene glycol mono-fatty acid ester, polyethylene glycol di-fatty acid ester and polyethylene glycol, the content of the polyethylene glycol in the product is up to 25% in 'preparation, properties and application of the polyethylene glycol fatty acid ester', and the high-content polyethylene glycol in the product has certain influence on the use of the product.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem that the content of polyethylene glycol in a fatty acid polyoxyethylene ester product obtained by a synthesis method for obtaining the fatty acid polyoxyethylene ester by polymerization reaction of ethylene oxide with fatty acid as an initiator in the prior art is high, and the invention provides a novel catalyst for synthesis of the fatty acid polyoxyethylene ester, wherein the catalyst has the characteristic of low content of polyethylene glycol in the fatty acid polyoxyethylene ester product.
The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst.
The invention aims to solve the third technical problem and provide a catalyst obtained by the preparation method of one of the technical problems.
The fourth technical problem to be solved by the invention is to provide the application of the catalyst.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
a catalyst for the synthesis of polyoxyethylene fatty acid ester, the catalyst comprising a quaternary ammonium compound and a transition metal oxide, the transition metal oxide comprising a metal selected from the group consisting of CoO, ZnO and La2O3At least one of the group of substances.
We have found that when the catalyst comprises both a quaternary ammonium compound and the transition metal oxide, there is an interaction promoting effect between the quaternary ammonium compound and the transition metal oxide in reducing the polyethylene glycol content of the product.
In the above technical scheme, the quaternary ammonium compound can be selected from quaternary ammonium salt and/or quaternary ammonium base.
In the above technical scheme, the structure of the quaternary ammonium compound preferably includes the following quaternary ammonium groups:
wherein R is1～R4Is independently selected from C1～C20A hydrocarbon group of (1). Such as but not limited to R1～R4Is independently selected from C1A hydrocarbon group of2A hydrocarbon group of3A hydrocarbon group of4A hydrocarbon group of5A hydrocarbon group of6A hydrocarbon group of7A hydrocarbon group of8A hydrocarbon group of9A hydrocarbon group of10A hydrocarbon group of11A hydrocarbon group of12A hydrocarbon group of13A hydrocarbon group of14A hydrocarbon group of15A hydrocarbon group of16A hydrocarbon group of17A hydrocarbon group of18And the like.
In the technical scheme, the total number of carbon atoms in the quaternary ammonium group is preferably 4-20.
In the above technical solution, the anion portion of the quaternary ammonium salt is not particularly limited, and for example, the quaternary ammonium salt may include at least one selected from the group consisting of chloride, bromide, and sulfate, and the like.
For comparison, the quaternary ammonium compounds in the practice of the present invention are chloride compounds.
In the above embodiment, the mass ratio of the transition metal oxide to the quaternary ammonium compound is preferably 0.05 to 20, for example, but not limited to, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.14, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 1.0, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 15, 19, and the like. The mass ratio of the transition metal oxide to the quaternary ammonium compound is more preferably 0.1 to 0.5.
In the above technical solution, the transition metal oxide preferably includes ZnO and CoO. ZnO and CoO have mutual enhancement effect on the aspect of reducing the content of polyethylene glycol in the fatty acid polyoxyethylene ester product. At this time, the specific ratio between ZnO and CoO is not particularly limited, and all can achieve comparable mutual enhancing effects. As non-limiting examples, the mass ratio of ZnO to CoO is 0.2 to 2.0, and further non-limiting examples of the mass ratio within this range may be 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, etc.; more preferably, the mass ratio is 0.3 to 0.6.
The preparation method of the catalyst of the present invention is not particularly limited, and may include simply mixing the quaternary ammonium compound and the transition metal oxide, and then using them in the synthesis of the polyoxyethylene fatty acid ester, or adding the quaternary ammonium compound and the transition metal oxide constituting the catalyst separately into the polymerization reaction system of the synthesis of the polyoxyethylene fatty acid ester, and when the quaternary ammonium compound and the transition metal oxide are added separately, there is no particular limitation on the order of adding them one after another or adding them at the same time, and all can achieve comparable technical effects.
However, in order to achieve the technical effect of better reducing the content of polyethylene glycol in the fatty acid polyoxyethylene ester product, i.e. to solve the second technical problem, the technical scheme of the invention is as follows:
the method for preparing the catalyst according to any one of the above technical problems, comprising:
(1) mixing the quaternary ammonium compound solution with a transition metal oxide to obtain a mixture I;
(2) and removing the solvent in the mixture I to obtain the catalyst.
In the above technical solutions, the solvent used for the quaternary ammonium compound solution is not particularly limited, and those skilled in the art can reasonably select the solvent without creative efforts, but water or a solvent mainly containing water is preferred.
In the above-mentioned embodiments, the concentration of the quaternary ammonium compound solution is not particularly limited, and any technical effect can be obtained. However, in view of economy, since the removal of the solvent in the step (2) requires energy, if the concentration is too small, the energy consumption for the removal of the solvent is increased.
The method for removing the solvent in the mixture I in the step (2) is not particularly limited, and for example, drying is carried out at a temperature of preferably 40 to 110 ℃ such as, but not limited to, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ and the like. If there is a clear liquid in mixture I, evaporation is selected prior to drying. The evaporation may be either atmospheric evaporation or vacuum evaporation, and is not particularly limited and may be appropriately selected by those skilled in the art. Reduced pressure evaporation may reduce the temperature of evaporation and/or increase the rate of evaporation. The temperature of the atmospheric evaporation is preferably 50 ℃ or higher to less than 100 ℃, for example, but not limited to, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or the like. It is generally preferred that the liquid be evaporated to no visibly apparent fluidity, as will be appreciated by those skilled in the art.
The technical key to the present invention is the selection of the components in the catalyst, and there is no particular limitation on the particle size of the quaternary ammonium compound and/or transition metal oxide, and those skilled in the art can reasonably select, for example, a particle size of more than 80 mesh in terms of mesh number. The particle sizes of the quaternary ammonium compound and the transition metal oxide are independently not limited to 100 mesh, 120 mesh, 150 mesh, 180 mesh, 200 mesh, 400 mesh, 600 mesh, 800 mesh, 1000 mesh, 2000 mesh, etc., expressed in mesh number, as non-limiting examples. However, the fine particles are advantageous for the performance of the catalyst.
In contrast, the quaternary ammonium compounds and/or transition metal oxides mentioned in the examples and comparative examples of the present invention were obtained as powders obtained by further pulverizing commercially available quaternary ammonium compounds and commercially available transition metal oxides and passing all through a 180-mesh sieve.
When the catalyst comprises the quaternary ammonium compound and the transition metal oxide, the order of adding the two components into the polymerization reaction system separately or adding the two components into the polymerization reaction system after mixing the two components is not particularly limited, and comparable technical effects can be obtained.
For the sake of comparability, when the catalyst in the embodiment of the present invention includes the quaternary ammonium compound and the transition metal oxide, both the quaternary ammonium compound and the transition metal oxide are separately pulverized and sieved, and then uniformly mixed in a desired ratio, and then used for the polymerization reaction.
To solve the third technical problem, the technical scheme of the invention is as follows:
a catalyst obtained by the production method described in any one of the two technical problems.
To solve the fourth technical problem, the technical scheme of the invention is as follows:
the catalyst according to any one of the above technical problems or the technical solution of the third technical problem is used in a synthesis method of fatty acid polyoxyethylene ester by polymerization of ethylene oxide using fatty acid as an initiator.
The technical scheme of the invention is the selection of the catalyst, and the technical conditions of the catalyst of the invention, which are particularly applied to the synthesis method of fatty acid polyoxyethylene ester, can be reasonably selected by a person skilled in the art without creative efforts, so the technical conditions given below in the specification of the invention are only preferred or exemplary.
In the technical scheme, the dosage of the catalyst is preferably 0.03-1% of the total mass of the theoretical product. Within this range, non-limiting specific point values may be, for example, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, 0.50%, 0.55%, 0.60%, 0.65%, 0.70%, 0.75%, 0.80%, 0.85%, 0.90%, and the like. More preferably, the dosage of the catalyst is 0.05-0.8% of the total mass of the theoretical product; most preferably, the amount of the catalyst is 0.2-0.3% of the total mass of the theoretical product.
In the above technical solution, the fatty acid is preferably C8～C18At least one of saturated or unsaturated fatty acids.Such as but not limited to one selected from the group consisting of C8Fatty acid, C9Fatty acid, C10Fatty acid, C11Fatty acid, C12Fatty acid, C13Fatty acid, C14Fatty acid, C15Fatty acid, C16Fatty acid, C17Fatty acids and C18At least one of the group of fatty acids. More specific examples of fatty acids include, but are not limited to, lauric acid, palmitic acid, oleic acid, stearic acid, and the like.
In the above technical solutions, the fatty acid may be a straight-chain fatty acid or a fatty acid having a branched chain, and the fatty acid is not particularly limited and can achieve comparable technical effects. Only by way of analogy, straight chain fatty acids were used in both the examples and comparative examples of the embodiments of the present invention.
In the technical scheme, the reaction temperature is preferably 110-180 ℃. For example, but not limited to, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C, etc. More preferably 130 to 150 ℃.
In the technical scheme, the feeding molar ratio of the ethylene oxide to the fatty acid is preferably 3-20. Such as, but not limited to, a molar ratio of 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and the like. More preferably, the feeding molar ratio of the ethylene oxide to the fatty acid is 5-13.
In the technical scheme, the polymerization reaction pressure is preferably 0-0.6 MPa. Such as, but not limited to, polymerization pressures of 0.05MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa, and the like. The polymerization pressure is more preferably 0 to 0.5 MPa.
In the technical scheme, the polymerization reaction time is preferably 1-8 hours. For example, but not limited to, polymerization times of 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, and the like. The polymerization time is preferably 3 to 5 hours.
The pressures in the present invention are gauge pressures.
Compared with the prior art, the content of polyethylene glycol impurities in the fatty acid polyoxyethylene ester product is obviously reduced after the method is adopted.
The content of the polyethylene glycol is measured by GB/T5560-2003 'measurement of the content of the polyethylene glycol and the content of a nonionic active substance (an addition product)'.
The present invention will be further described with reference to the following examples.
Detailed Description
[ example 1 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of n-octanoic acid and 1.44g of catalyst were put into a 2L reactor equipped with a stirring, electric heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when the total amount of the ethylene oxide is 274.6g, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 2 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of n-octanoic acid and 2.58g of catalyst were put into a 2L reactor equipped with a stirring, electric heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 732.3g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 3 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of n-octanoic acid and 4.18g of catalyst were put into a 2L reactor equipped with a stirring, electric heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 1373.0g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 4 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of lauric acid and 2.07g of catalyst were put into a 2L reactor equipped with a stirring, electric heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when the total amount of the ethylene oxide is 527.2g, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 5 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of lauric acid and 2.07g of catalyst were put into a 2L reactor equipped with a stirring, electric heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when the total amount of the ethylene oxide is 527.2g, carrying out curing reaction at 120 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 6 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of lauric acid and 2.07g of catalyst were put into a 2L reactor equipped with a stirring, electric heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when the total amount of the ethylene oxide is 527.2g, carrying out curing reaction at 160 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 7 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 0.67g of catalyst were placed in a 2L reactor equipped with a stirring, electric heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 8 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 2.70g of catalyst were placed in a 2L reactor equipped with a stirring, electric heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 9 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 10 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 11 ]
1. Catalyst preparation
Crushing commercially available CoO powder, and sieving all the powder by a 180-mesh sieve; adding the sieved CoO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to CoO is 1:0.5), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the CoO of 1: 0.5.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃ and carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃ and maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 12 ]
1. Catalyst preparation
Crushing commercially available ZnO powder, and sieving the powder with a 180-mesh sieve; adding the sieved ZnO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to ZnO is 1:0.25), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the ZnO of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃ and carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃ and maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 13 ]
1. Catalyst preparation
Will market La2O3Pulverizing the powder, and sieving with 180 mesh sieve; taking the sieved La2O3Adding the powder into 20 wt% aqueous solution of tetramethylammonium chloride (tetramethylammonium chloride and La)2O3The mass ratio of (1: 0.25) and stirring uniformly, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying at 50 deg.C for 8 hr, pulverizing, and sieving with 180 mesh sieve to obtain tetramethylammonium chloride and La2O3In a mass ratio of 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃ and carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃ and maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 14 ]
1. Catalyst preparation
Respectively pulverizing commercially available CoO and ZnO, and sieving with 180 mesh sieve; respectively adding the sieved CoO and ZnO powder into a tetramethylammonium chloride aqueous solution with the weight concentration of 20% (the mass ratio of tetramethylammonium chloride to a transition metal oxide is 1:0.25, wherein the mass ratio of CoO to ZnO contained in the transition metal oxide is 1: 0.45), uniformly stirring, and standing for half an hour; stirring and evaporating at 90 ℃ until no visible flowing liquid exists; drying for 8 hours at 50 ℃, crushing and sieving with a 180-mesh sieve to obtain the powdery catalyst with the mass ratio of the tetramethylammonium chloride to the transition metal oxide being 1: 0.25.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ example 15 ]
The process conditions were the same as in example 9, except that the catalyst was obtained by simple mixing, specifically:
1. catalyst preparation
Mixing the tetramethylammonium chloride crushed and sieved by a 180-mesh sieve and the CoO crushed and sieved by the 180-mesh sieve according to the mass ratio of the tetramethylammonium chloride to the CoO of 1:0.25, and is used as a catalyst.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
In comparison with example 9, it can be seen that the catalyst obtained by the preparation method according to the second technical aspect of the present invention has a better technical effect in reducing the content of polyethylene glycol in the fatty acid polyoxyethylene ester product.
[ COMPARATIVE EXAMPLE 1 ]
1. Catalyst preparation
Granular potassium hydroxide on the market is directly used as a catalyst without being crushed.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ COMPARATIVE EXAMPLE 2 ]
1. Catalyst preparation
Commercially available tetramethylammonium chloride was pulverized and the whole was passed through a 180 mesh sieve as a catalyst.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ COMPARATIVE EXAMPLE 3 ]
1. Catalyst preparation
Commercial CoO was crushed and the whole was passed through a 180 mesh sieve as a catalyst.
2. Synthesis of polyoxyethylene fatty acid ester
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ COMPARATIVE EXAMPLE 4 ]
1. Catalyst preparation
Commercial ZnO was pulverized and the whole was passed through a 180 mesh sieve as a catalyst.
2. Synthesis of polyoxyethylene fatty acid ester 300.0g of oleic acid and 1.68g of catalyst are put into a 2L reaction kettle with a stirring and electric heating jacket and an internal water-cooling coil pipe, and the reaction kettle is sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃ and carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃ and maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
[ COMPARATIVE EXAMPLE 5 ]
1. Catalyst preparation
Will market La2O3Pulverizing, and sieving with 180 mesh sieve to obtain the final product.
300.0g of oleic acid and 1.68g of catalyst were placed in a 2L reactor equipped with a stirring, electrical heating jacket and an internal water-cooled coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 373.8g of the total ethylene oxide is introduced, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 40 ℃ to obtain the fatty acid polyoxyethylene ester product.
For ease of comparison, the main operating conditions and the measured polyethylene glycol content of the fatty acid polyoxyethylene ester product are listed in table 1.
TABLE 1
#: example 15 the process conditions were the same as in example 9 except that the catalyst was simply mixed.
Claims (11)
1. A catalyst for the synthesis of polyoxyethylene fatty acid ester, said catalyst being selected from the following scheme 1 or scheme 2:
scheme 1: the catalyst consists of quaternary ammonium compound and transition metal oxide, and the transition metal oxide is at least one selected from the group consisting of CoO and ZnO;
scheme 2: the catalyst comprises a quaternary ammonium compound and a transition metal oxide, the transition metal oxide comprising La2O3。
2. Catalyst according to claim 1, characterized in that the quaternary ammonium compound is a quaternary ammonium salt and/or a quaternary ammonium base.
3. The catalyst of claim 1, wherein the quaternary ammonium compound comprises the following quaternary ammonium groups in its structure:
wherein R is1～R4Is independently selected from C1～C20A hydrocarbon group of (1).
4. A catalyst according to claim 3, characterised in that the total number of carbon atoms in the quaternary ammonium group is from 4 to 20.
5. The catalyst according to claim 2, wherein the quaternary ammonium salt comprises at least one selected from the group consisting of chloride, bromide and sulfate.
6. The catalyst according to claim 1, wherein the mass ratio of the transition metal oxide to the quaternary ammonium compound is 0.05 to 20.
7. The catalyst according to claim 6, wherein the mass ratio of the transition metal oxide to the quaternary ammonium compound is 0.1 to 0.5.
8. The catalyst of claim 1, wherein the transition metal oxide in scheme 1 comprises ZnO and CoO.
9. The catalyst according to claim 8, wherein the mass ratio of ZnO to CoO is 0.2 to 2.0.
10. The catalyst according to claim 9, wherein the mass ratio of ZnO to CoO is 0.3 to 0.6.
11. Process for the preparation of the catalyst according to claim 1, comprising:
(1) mixing the quaternary ammonium compound solution with a transition metal oxide to obtain a mixture I;
(2) and removing the solvent in the mixture I to obtain the catalyst.
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| EP0783012A1 (en) * | 1995-12-22 | 1997-07-09 | Kao Corporation | Process for producing ester alkoxylate compound and surfactant comprising ester alkoxylate compound |
| CN101402736A (en) * | 2008-11-12 | 2009-04-08 | 华中科技大学 | Biodegradable unsaturated polyphosphate, preparation and use method thereof |
| CN103881079A (en) * | 2012-12-24 | 2014-06-25 | 青岛帅王油脂化学有限公司 | Polyoxyethylene ether stearate preparation method |
| CN106831701A (en) * | 2016-12-08 | 2017-06-13 | 盐城利庞新型材料科技有限公司 | The preparation method and its catalyst of sulfuric acid vinyl ester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0783012A1 (en) * | 1995-12-22 | 1997-07-09 | Kao Corporation | Process for producing ester alkoxylate compound and surfactant comprising ester alkoxylate compound |
| CN101402736A (en) * | 2008-11-12 | 2009-04-08 | 华中科技大学 | Biodegradable unsaturated polyphosphate, preparation and use method thereof |
| CN103881079A (en) * | 2012-12-24 | 2014-06-25 | 青岛帅王油脂化学有限公司 | Polyoxyethylene ether stearate preparation method |
| CN106831701A (en) * | 2016-12-08 | 2017-06-13 | 盐城利庞新型材料科技有限公司 | The preparation method and its catalyst of sulfuric acid vinyl ester |
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